Proton exchange membrane water electrolysis (PEMWE) performs the electrolysis of water to produce hydrogen, a source of clean and renewable energy. The most used commercial electrolyte in PEMWE is the Nafion membrane, a material that is expensive and difficult to recycle. The partial replacement of Nafion with cellulose nanocrystals (CNCs) can produce composite membranes can increased electrical, mechanical and biodegradability properties. In this sense, the objective of this work is to study the elaboration of nanocomposites (Nafion-CNC) aiming at developing high-performance electrolytes for application in PEMWE. The effects of adding CNCs to Nafion were evaluated. Nafion membranes were produced with two types of CNCs, one obtained by enzymatic hydrolysis and the other by acid hydrolysis (commercial). The addition of both CNCs has similar effects on Nafion's properties. For samples with both commercial and enzymatic CNC, an increase in the modulus of elasticity (10% and 40% respectively) and maximum stress (10% and 13% respectively) was observed. The two nanocomposites showedlower initial thermal degradation temperatures, however, they still showed sufficient stability (Tonset gt; 170°C) for application in PEMWE (standard operating temperature lt;100°C). Furthermore, there was a significant increase in the humidification capacity and increase in conductivity. Composite membranes were tested in PEMWE and their usability was proven.

La electrólisis del agua con membrana de intercambio de protones (PEMWE) realiza la electrólisis del agua para producir hidrógeno, una fuente de energía limpia y renovable. El electrolito comercial más utilizado en PEMWE es la membrana Nafion, un material caro y difícil de reciclar. El reemplazo parcial de Nafion con nanocristales de celulosa (CNC) puede producir membranas compuestas que pueden aumentar las propiedades eléctricas, mecánicas y de biodegradabilidad. En este sentido, el objetivo de este trabajo es estudiar la elaboración de nanocompositos (Nafion-CNC) con el objetivo de desarrollar electrolitos de alto rendimiento para su aplicación en PEMWE. Se evaluaron los efectos de agregar CNC a Nafion. Las membranas de Nafion se produjeron con dos tipos de CNC, uno obtenido por hidrólisis enzimática y el otro por hidrólisis ácida (comercial). La adición de ambos CNC tiene efectos similares en las propiedades de Nafion. Para muestras con CNC tanto comerciales como enzimáticas, se observó un aumento en el módulo de elasticidad (10% y 40% respectivamente) y tensión máxima (10% y 13% respectivamente). Los dos nanocompuestos mostraron temperaturas iniciales de degradación térmica más bajas, sin embargo, aún mostraron suficiente estabilidad (Tonset gt; 170 °C) para su aplicación en PEMWE (temperatura de operación estándar lt;100 °C). Además, hubo un aumento significativo en la capacidad de humidificación y un aumento en la conductividad. Las membranas compuestas se probaron en PEMWE y se comprobó su usabilidad.

A eletrólise da água com membrana de troca de prótons (PEMWE) realiza a eletrólise da água para produzir hidrogênio, uma fonte de energia limpa e renovável. O eletrólito comercial mais utilizado no PEMWE é a membrana de Nafion, um material caro e de difícil reciclagem. A substituição parcial do Nafion por nanocristais de celulose (CNCs) pode produzir membranas compostas com propriedades elétricas, mecânicas e de biodegradabilidade aumentadas. Nesse sentido, o objetivo deste trabalho é estudar a elaboração de nanocompósitos (Nafion-CNC) visando o desenvolvimento de eletrólitos de alto desempenho para aplicação em PEMWE. Os efeitos da adição de CNCs ao Nafion foram avaliados. As membranas de nafion foram produzidas com dois tipos de CNCs, um obtido por hidrólise enzimática e outro por hidrólise ácida (comercial). A adição de ambos os CNCs tem efeitos semelhantes nas propriedades do Nafion. Para amostras com CNC comercial e enzimática, observou-se um aumento no módulo de elasticidade (10% e 40% respectivamente) e tensão máxima (10% e 13% respectivamente). Os dois nanocompósitos apresentaram menores temperaturas iniciais de degradação térmica, porém, ainda apresentaram estabilidade suficiente (Tonset gt; 170°C) para aplicação em PEMWE (temperatura padrão de operação lt;100°C). Além disso, houve um aumento significativo na capacidade de umidificação e aumento na condutividade. As membranas compostas foram testadas em PEMWE e sua usabilidade foi comprovada.

ABSTRACT: Due to their remarkable characteristics, cellulose nanocrystals are strategic materials that has various industrial applications, and are capable of being produced from vegetable fibers derived from the discards of agricultural practices. Peanut(Arachis hypogaea L.) peel is a residue considered of low commercial value and high polluting potential that needs new applications in order to mitigate these problems. Thus, in this study the feasibility of extracting cellulose nanocrystals was investigated. Two chemical routes were followed for this extraction. In the first, the fibers were bleached before acid hydrolysis whereas mercerization was used in the second. The second route was more efficient, as it enabled the elimination of proteins and phenolic compounds, which could be confirmed through solid-state 13C nuclear magnetic resonance (NMR) that revealed no signs of lignin residues. The cellulose nanocrystals composed of mainly type I cellulose presented a high degree of crystallinity index, 75 %, a thermal stability up to 200 °C, considerable stability in suspension (zeta potential of –48.1 ± 2.1 mV), and an aspect ratio of 125. They represent options that could add value to this residue, which would ease environmental problems.

Biomaterials have been intensively investigated due to the increase in the elderly population and high prevalence of several disorders, such as cardiovascular and orthopedic diseases. Polymeric and composite polymeric materials in combination with different processing techniques, such as electrospinning, solution blow spinning, ultrathin film preparation, and 3D printing are promising for obtaining biomaterials with patient-specific applications. Here, we provide a review on recent advances and perspectives for synthetic and natural polymers as well as composites in the design of biomaterials. After introducing basic information about biomaterials, we describe the fundamentals of manufacturing techniques and highlight possible biomedical applications.

Abstract Blends of zein and poly(vinyl alcohol) (PVAl) were processed in an internal mixer (150ºC, 50 rpm) for 5-8 minutes. Glycerol and oleic acid were used as plasticizers. The mixtures obtained were then compression molded and further characterized by Fourier transform infrared spectroscopy (FTIR), water-absorption experiments, mechanical tests, and scanning electron microscopy (SEM). FTIR analysis indicated the existence of hydrogen bonding interactions between zein and PVAl. Tensile tests showed that the addition of PVAl increased the flexibility of the blends. The tensile strength ranged from 1.7 to 5.7 MPa, elongation at break ranged from 2.7 to 32% and Young’s modulus ranged from 433 to 7371 MPa. Water absorption at equilibrium decreased with increasing zein content, which favored a brittle behavior in the zein/PVAl. The blends were immiscible in the composition studied and the presence of voids indicated poor interfacial interaction between the polymers.

Abstract The non-isothermal decomposition kinetics of conductive polyaniline (PANI) and its derivatives, poly(o-methoxyaniline) (POMA) and poly(o-ethoxyaniline) (POEA), was investigated by thermogravimetric analysis (TGA), under inert and oxidative atmospheres, using Flynn-Wall-Ozawa’s approach to assess the kinetic parameters of the decomposition process. The order of reaction was found to be dependent on the degree of conversion indicating that both the early and the later stages of polymer degradation were next the zero or pseudo zero order kinetics, whereas the intermediate stages follow a first order kinetics. The activation energy was found to be dependent on both the degree of conversion and PANI derivative. Activation energy values vary from 125 to 250 kJ/mol, to decompositions carried out under nitrogen, and 75 to 120 kJ/mol to oxidative atmosphere. Parent PANI presented the best thermal stability and suggesting that thermal stability is also influenced by derivatization and type of atmosphere used.

Thermoplastic starch properties depends of plastification process. The aim of this study was to analyze the effect of concentration of glycerol and water on plastification, glass transition temperature (Tg) and tensile properties of thermoplastic waxy starch (TPWS). Formulations were extruded in the following concentrations of starch/glycerol/water: 70/30/0 (TPWS 0%); 70/25/5 (TPWS 5%); 70/20/10 (TPWS 10%) weight percentage. Crystalline peaks in WAXS diagrams and native grains present in SEM micrographs showed that the TPWS 0% and 5% were not sufficient to promote total plastification of the waxy starch, and TPWS 10% showed the higher starch plastification. Tg measurements by DMTA were 30 ºC to TPWS 0%, 23 ºC to TPWS 5% and 40 ºC to TPWS 10%. These results showed that glycerol and water had effect plasticizer in TPWS 5% and antiplasticizer in TPWS 10%. Mechanical tensile results showed that higher tensile strength was observed in the systems with more effective starch plastification.

Abstract This paper reports on a study of highly filled composites of polypropylene (PP) and 75% by weight sugarcane bagasse fiber with and without alkali treatment and with and without coupling agent (SEBS-g-MA). Composites were prepared using a Rheomix600 mixer connected to a HAAKE torque rheometer. The thermal and mechanical behavior of these composites were investigated by thermogravimetry (TGA), differential Scanning Calorimetry (DSC), flexural tests, impact tests and scanning electron microscopy. Scanning electron microscopy (SEM) images taken from sugarcane bagasse fibers showed enhancements in the fiber's surface topography after the surface treatment process. The FTIR, TGA and SEM results for the fibers showed that the alkali treatment modified the fiber surface as well as the chemical composition. The impact test results showed a good potential of SEBS-g-MA as coupling agent and impact modifier in highly filled composites, increasing by more than 100% the impact strength of the composite as compared to those without the coupling agent. Scanning electron microscopy showed that addition of coupling agent improved the interfacial adhesion between the fibers and polypropylene.

RESUMO O isolamento de nanocristais de celulose (CNCs) de fibras vegetais é uma alternativa promissora para sua aplicação como reforço em matrizes poliméricas. A caracterização dos CNCs é fundamental para a confiabilidade da técnica, além de determinar as aplicações possíveis a partir de cada tipo de fibra. A partir da técnica de microscopia de força atômica, um estudo da morfologia e distribuição dos CNCs de semente de manga, vagem de algaroba, pseudocaule da bananeira e fibra do mesocarpo de dendê foi realizado neste trabalho. Os CNCs foram obtidos via reação hidrolítica com ácido sulfúrico em concentrações que variaram de acordo com a fonte da fibra. Os resultados obtidos revelaram dimensões variando de 300 a 500 nm em comprimento e 4 a 16 nm em diâmetro. A apresentação morfológica em forma de agulha demonstrou que o isolamento das fibras de celulose em CNCs foi efetiva. A razão de aspecto associada à formação cilíndrica em agulha dos CNCs isolados evidenciou o alto potencial das fontes de dendê e de vagem de algaroba para o reforço de bionanocompósitos.

ABSTRACT The isolation of vegetables fiber in cellulose nanocrystals (CNCs) comprises a promising alternative for application as reinforcement in polymer matrices. The characterization of the CNCs is essential to evaluate the reliability of this technique and to determine the possible applications from each vegetable fiber type. Therefore it is proposed here a study with atomic force microscopy technique to analyze the morphology and distribution of CNCs from mango seed, mesquite pods, banana pseudostem and fiber palm mesocarp. CNCs were obtained by acid hydrolysis with sulfuric acid in concentrations that varied according to the fiber sources. The results showed dimensions ranging from 300 to 500 nm in length and 4 to 16 nm in diameter. The morphology obtained needle-like show that the isolation of cellulose fibers to CNCs was. The aspect ratio related to the cylindrical needle organization of the isolated CNCs indicate the high potential of the palm mesocarp and mesquite pods as reinforcement on bionanocomposites.

Resumo Este trabalho propõe um novo método de produção de filmes estáveis para aplicações em sensores baseado na deposição pela técnica de automontagem de poli(o-etoxianilina) alternada com fenol-formaldeído (POEA/PF) seguida por cura térmica. O processo de reticulação foi caracterizado por espectroscopias no infravermelho por transformada de Fourier e no ultravioleta-visível, microscopia de força atômica e estudos de dessorção; a capacidade sensorial destes filmes foi avaliada através de medidas em sensores. Os resultados mostram que a resina PF serviu como agente de cura e alternante formando uma rede semi-interpenetrante, por conseguinte, filmes mais estáveis foram produzidos. Embora tenha ocorrido uma diminuição da sensibilidade dos sensores com o reticulação, tais filmes são bastante estáveis e podem ser potencialmente usados em sensores, especialmente onde uma maior estabilidade se faz necessária.

Abstract A new method for producing stable films used in sensors is proposed, based on the layer-by-layer deposition of poly(o-ethoxyaniline) and phenol-formaldehyde (POEA/PF) followed by a thermal treatment to promote film crosslinking. The crosslinking process was characterized by Fourier transform infrared and ultraviolet-visible spectroscopic analyses, atomic force microscopy and desorption studies. Sensor analyses were also carried out in order to evaluate cross-linked sensor signal. Results showed that PF resin served as a curing agent, forming a semi-interpenetrating polymer network therefore producing stable films. Although there was a decrease in the sensitivity of sensors with crosslinking, such films are quite stable and can be potentially used in sensors, especially where higher stability is required.

Neste trabalho, o objetivo foi produzir nanobiocompósitos biodegradáveis à base de pectina e nanoemulsão de canela que tenham propriedades satisfatórias para aplicação como embalagens ativas. Foram detalhados os procedimentos de preparação das nanoemulsões e incorporação dessas na matriz polimérica. Foi apresentada uma metodologia nova de análises dos melhores nanocompósitos através de um planejamento baseado em aspectos visuais que nos forneceu resultados interessantes. Os nanocompósitos obtidos foram analisados através de: medidas de espessura, solubilidade, propriedades mecânicas e microscopia eletrônica de varredura (MEV). Resultados das análises visuais mostraram que os nanocompósitos produzidos com concentração de pectina de 2% m/v e nanoemulsões preparadas com velocidade de agitação de 16000 rpm em 2 minutos mostraram melhores condições para serem aplicados como embalagens. Resultados de propriedades mecânicas demonstraram que nanocompósitos contendo nanoemulsões com tamanhos menores de gotículas apresentam maior resistência e elongação, além de serem menos solúveis. O controle dessas propriedades com a variação de tamanho médio das nanoemulsões torna esses materiais potencialmente viáveis, por exemplo, em embalagens ativas.

In this study, the objective was to produce biodegradable nanobiocomposites based on pectin and cinnamon nanoemulsion having satisfactory properties for application as active packaging. Procedures for preparing and incorporating these nanoemulsions in the polymeric matrix are described. The nanocomposites were analyzed through: thickness measurements, solubility, mechanical properties and scanning electron microscopy (SEM). A subjective analysis indicated the nanocomposite made with pectin 2 % w/v and nanoemulsions prepared with stirring speed of 16000 rpm in 2 min was the most suitable for application in packaging. The nanocomposites containing nanoemulsions with smaller nanodroplets had greater strength and elongation, being less soluble. The control of these properties by varying the average size of the nanoemulsion makes these materials potentially viable, for example, for active packaging.

Nesse trabalho a influência do porta-enxerto sobre o enxerto nas amostras de látex (Hevea brasiliensis) foi verificada através da análise de RMN de ¹H e análise multivariada dos dados. Através da análise de RMN de ¹H foi possível caracterizar 16 metabólitos presentes no citosol do látex. A análise de PCA mostrou que as amostras de látex dos grupos RR e GG podem ser diferenciadas. As amostras do grupo GR possuem perfil metabólico semelhante às amostras do grupo RR, enquanto o grupo RG situa-se em posição intermediária entre os grupos RR e GG. A sacarose e o formiato contribuíram em grande parte pela separação obtida por PCA e apresentaram boa correlação com os resultados obtidos. A RMN de ¹H provou ser uma técnica eficiente na diferenciação entre amostras provenientes de diferentes tipos de porta-enxerto e enxerto e pode futuramente ser utilizada para prever a produção de borracha através da análise do látex.

In this study, the effect of rootstock on grafting through metabolomic analysis of latex (Hevea brasiliensis) samples was verified by ¹H nuclear magnetic resonance (NMR) and multivariate data analysis. Sixteen metabolites present in the latex cytosol were characterized by NMR. PCA analysis showed that the latex samples of the RR and GR groups can be differentiated. The GR group samples present a metabolic profile similar to the RR group samples, while the RG group is in an intermediate position between RR and GG groups. Sucrose and formate contributed greatly to the separation obtained by PCA, presenting a good correlation between the results. ¹H NMR was an efficient technique to differentiate latex samples from different types of rootstocks and grafting and in the future could be used to predict rubber production by latex analysis.

Poly(vinylidene fluoride)/polyaniline blends of different composition were synthesized by chemical polymerization of aniline in a mixture of Poly(vinylidene fluoride) and N,N-dimethylformamide and their thermal and mechanical behavior was investigated as a function of the polyaniline doping level and the composition using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis and tensile tests techniques. The results showed the blend obtained presents a good thermal stability with low weight loss up to 300 ºC, assigned to water and solvents evaporation. The glass transition and melting point is not affected by the PANI content in the blend, showing that polymers are no miscible. The films produced present a good sustainability; however the presence of the conducting polymer in the blend increases the tensile strength and the Young modulus, while diminishes the elongation at break, as compared to pure PVDF.

A agroindústria do açaí gera uma grande quantidade de resíduos, constituída de caroços e fibras, o que é um grave problema ambiental e de saúde pública. O objetivo deste estudo foi estudar as fibras do mesocarpo e o caroço do fruto do açaí para sua utilização em materiais compósitos. As amostras foram caracterizadas usando análise por termogravimetria (TG/DTG) em atmosferas inerte e oxidativa, microscopia eletrônica de varredura e microscopia óptica. As fibras apresentaram boa estabilidade térmica até 230 ºC e um processo de degradação em atmosfera inerte em três etapas. Em atmosfera oxidativa, as fibras apresentaram menor estabilidade térmica e uma mudança no processo de degradação de três para quatro etapas. os resultados da análise térmica do caroço mostraram um comportamento térmico similar ao da fibra. A microscopia mostrou que as fibras presentes no fruto do açaí recobrem o caroço e possuem morfologia irregular com a presença de células do parênquima na sua superfície. O comportamento térmico das fibras do açaí é semelhante ao de outras fibras vegetais já utilizadas industrialmente na área de compósitos poliméricos, o que abre novas e promissoras áreas para sua utilização.

The açaí fruit agro industry produces a large amount of waste, mainly seeds and fibers, which is a serious environmental and public health problem. The aim of this work is to study the mesocarp fibers and the açaí fruit seed to use in composite materials. The samples have been characterized by using thermogravimetric analysis (TGA/DTG) in inert and thermo-oxidative atmospheres, scanning electron and optical microscopy. The fibers have shown good stability until 230ºC and a threedegradation step process in inert atmosphere. In oxidative atmosphere, the fibers presented a decrease in thermal stability and a change in the decomposition process from three to four steps. For the seeds, a similar behavior was observed, although a lower thermal stability was observed when compared to the fiber. Longitudinal morphology of the fibers that cover the açaí seed is rough, and parenchyma cells can be seen on the surface. The açaí fibers exhibited a thermal behavior comparable to other natural fibers used in composites, which is promising for new applications.

O consumo da água de coco verde, in natura ou industrializada, vem gerando um grande problema ambiental, devido ao destino final da casca dos frutos. Aproximadamente 85% do peso bruto do coco verde é constituído pelas cascas, que são acumuladas em lixões ou às margens de estradas. Como a minimização da geração desse resíduo implicaria a redução da atividade produtiva associada, o seu aproveitamento torna-se uma necessidade. Neste sentido, este estudo teve como objetivo investigar as características da fibra de coco verde de diversos cultivares em função do ponto de colheita dos frutos, na composição química, nas propriedades mecânicas e térmicas, como forma de contribuir para avaliar seu potencial de aplicação na elaboração de novos materiais. Os resultados mostraram que a variação da composição química em função da cultivar de coco verde foi na faixa de 37,2 ± 0,8% a 43,9±0,7% e de 31,5±0,1% a 37,4±0,5% para os teores de lignina e celulose, respectivamente. A composição química não variou significativamente em função do ponto de maturação para a fibra da cultivar Anão-Verde-de-Jiqui (AVeJ). A fibra de cultivares de coco verde e AVeJ em diferentes pontos de maturação apresentaram propriedades térmicas e mecânicas semelhantes, as quais são próximas das propriedades das fibras de coco maduro, demonstrando, portanto, um potencial equivalente para serem utilizadas como reforço em matrizes poliméricas.

The consumption of water of green coconut in natura or industrialized has generated a large amount of residues that are disposed in landfills or in roadside. The husks residues correspond to around 85% of the weight of the fruit and present slow decomposition process. This environmental problem requires alternative solutions. In order to assessing to potential of the immature (green) coconut fibers to be used as reinforcement material in polymer matrices, the chemical composition, thermal and mechanical characteristics of the coconut fibers originated from 5 immature coconut cultivars of the Nana variety at 4 different ages were studied. According to the results obtained, the change of the chemical composition with the cultivar was from 37.2 ± 0.8% to 43.9±0.7% and from 7.4±0.5% to 31.5±0.1% for lignin and cellulose contents, respectively. The age did not significantly influence the chemical composition of 'Anão Verde de Jequi' (AVeJ) cultivar. All the cultivars and AVeJ, in different ages showed approximately the same thermal and mechanical behaviors, which were similar to the mature coconut fiber properties. This study shows that the immature cultivars studied offer potential to be used as reinforcement in composites similarly to mature coconut fiber.

Hidrogéis produzidos a partir de poliacrilamida (PAAm) foram sintetizados e suas eficiências para liberação controlada de NH4+ e K+ contidos em fertilizantes foram avaliadas. Os hidrogéis foram sintetizados em solução aquosa a partir da polimerização do monômero acrilamida (AAm) em duas concentrações (3,6 e 21,7 %), em presença do agente de reticulação N', N-metileno-bis-acrilamida (MBAAm) e catalisador N, N, N', N'-tetrametil etilenodiamina (TEMED). A fixação de nutrientes ocorreu submetendo-se os hidrogéis à solução aquosa com concentrações de 86 e 82 mg L-1 de K+ e NH4+. As propriedades hidrofílicas, espectroscópicas e morfológicas foram investigadas por meio de medidas de grau de intumescimento (Q), por espectroscopia no infravermelho com transformada de Fourier (FTIR) e por meio de imagens obtidas por microscopia eletrônica de varredura (MEV). Os teores de NH4+ e K+ liberados em meio aquoso foram monitorados em intervalos de tempo de 1, 2, 4, 18, 26 e 50 h por espectrofotometria com análise por injeção em fluxo e por fotometria de chama. Os resultados de grau de intumescimento mostraram que hidrogéis com nutrientes fixados são mais hidrofóbicos. Observações em MEV revelaram decréscimo no tamanho médio dos poros para os hidrogéis com maior quantidade de acrilamida. A cinética de liberação controlada de NH4+ e K+ permitiu inferir que o hidrogel sintetizado com 21,7 % de AAm apresentou maior potencial na liberação controlada dos nutrientes, principalmente NH4+.

Hydrogels based on polyacrylamide (PAAm) were synthesized and their efficiency for the controlled release of ammonium and potassium contained in fertilizers evaluated. The hydrogels were synthesized by polymerizing acrylamide (AAm) in aqueous solution at two acrylamide concentrations (3.6 and 21.7 %) using N-N'-methylene-bisacrylamide (MBAAm) as cross-linker and N,N,N',N' tetramethylethylenediamine (TEMED) as catalytic agent. Nutrient fixation was performed by immersion of hydrogels in aqueous nutrient solutions with 86 and 82 mg L-1 K+ and NH4+. The hydrophilic, spectroscopic and morphological properties were investigated based on the swelling degree (Q) and Fourier-transform infrared spectroscopy (FTIR), and images obtained using scanning electron microscopy (SEM). The amount of NH4+ and K+ released in aqueous solution was monitored at intervals of 1, 2, 4, 18, 26, and 50 h by spectrometry, using a flow injection analysis system, and by flame photometry. The swelling degree results show that hydrogels with fixed nutrients are more hydrophobic. SEM images revealed a significant decrease in the average porous size of hydrogels with higher acrylamide content. The release kinetics of NH4+ and K+ allowed to conclude that hydrogel synthesized with 21.7 % AAm had a higher nutrient release potential, especially NH4+.